WO2006106731A1 - Batterie secondaire cylindrique au lithium - Google Patents

Batterie secondaire cylindrique au lithium Download PDF

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Publication number
WO2006106731A1
WO2006106731A1 PCT/JP2006/306459 JP2006306459W WO2006106731A1 WO 2006106731 A1 WO2006106731 A1 WO 2006106731A1 JP 2006306459 W JP2006306459 W JP 2006306459W WO 2006106731 A1 WO2006106731 A1 WO 2006106731A1
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WO
WIPO (PCT)
Prior art keywords
battery
resistant layer
porous heat
lithium secondary
secondary battery
Prior art date
Application number
PCT/JP2006/306459
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English (en)
Japanese (ja)
Inventor
Masato Fujikawa
Kohei Suzuki
Kaoru Inoue
Mikinari Shimada
Original Assignee
Matsushita Electric Industrial Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Matsushita Electric Industrial Co., Ltd. filed Critical Matsushita Electric Industrial Co., Ltd.
Priority to EP06730407A priority Critical patent/EP1768202A1/fr
Priority to CN2006800009067A priority patent/CN101032044B/zh
Publication of WO2006106731A1 publication Critical patent/WO2006106731A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a lithium secondary battery having a high degree of safety, which is excellent in short circuit resistance and heat resistance, and mainly relates to a technology for preventing a capacity decrease due to an impact such as falling.
  • Lithium secondary batteries are attracting attention as high-capacity power supplies mainly in portable devices.
  • a chemical battery including a lithium secondary battery has a separator which has a function of electrically insulating the positive electrode and the negative electrode and retaining the electrolyte.
  • a lithium secondary battery it is mainly used as a microporous film force separator that can also function as a polyolefin (eg, polyethylene, polypropylene, etc.).
  • An electrode assembly of a cylindrical lithium secondary battery is formed by winding a positive electrode and a negative electrode together with a separator interposed therebetween in a cylindrical shape. At that time, a predetermined cavity is formed at the center of the electrode group. In the process of manufacturing the battery, when the electrode group is impregnated with the non-aqueous electrolyte, the non-aqueous electrolyte is injected into the central cavity of the electrode group.
  • Electrodes in the electrode group expand or contract with charge and discharge. Therefore, the electrode group tends to gradually deform from its initial shape. Therefore, it has been proposed to press the electrode group from its center to prevent deformation of the electrode group (further, breakage of the electrode due to the deformation)! (See Patent Document 1).
  • Patent Document 2 a simple structure has also been proposed in which a hollow core rod is inserted into a hollow portion at the center of the electrode group (Patent Document 2).
  • the core rod is provided with a longitudinal slit along its entire length. The non-aqueous electrolyte injected into the central cavity of the electrode assembly is introduced into the electrode assembly through the slits.
  • the separator made of the microporous film is easily shrunk.
  • an internal short circuit may occur in which the positive electrode and the negative electrode physically contact.
  • the separator tends to be thinner. Therefore, prevention of internal short circuit Forces are becoming more important. Once an internal short circuit occurs, the Joule heat associated with the short circuit current causes the short circuit to expand, which may lead to the battery overheating.
  • a porous heat-resistant layer containing an inorganic filler (solid fine particles) and a binder is supported on the electrode active material layer from the viewpoint of suppressing the expansion of the short circuit portion.
  • an inorganic filler alumina, silica or the like is used.
  • the porous heat-resistant layer is filled with an inorganic filler, and the filler particles are bonded with a relatively small amount of a binder (Patent Document 3).
  • the porous heat-resistant layer is difficult to shrink even at high temperatures, and therefore serves to suppress overheating of the battery when an internal short circuit occurs.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 11-224689
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2003-317805
  • Patent Document 3 Japanese Patent Application Laid-Open No. 7-220759
  • Patent Document 1 or 2 In order to realize an excellent lithium secondary battery, it is conceivable to use the proposal of Patent Document 1 or 2 and the proposal of Patent Document 3 in combination. As a result, deterioration of the electrode group is suppressed, and internal short circuit defects are significantly reduced. However, when a shock is applied to the battery due to a drop or the like, a noticeable capacity reduction may occur.
  • the present invention covers a cylindrical battery can having a bottom portion, a side wall and an upper opening, an electrode assembly, a non-aqueous electrolyte, and an electrode assembly containing the electrode assembly and a non-aqueous electrolyte.
  • a lithium secondary battery including a plate, wherein the electrode group is formed by winding a strip-like positive electrode and a strip-like negative electrode together with a porous heat-resistant layer and a separator interposed therebetween; Material and a positive electrode active material layer supported on both sides thereof, the negative electrode includes a negative electrode core material and a negative electrode active material layer supported on both sides thereof, and the electrode group has a cavity in the center, A hollow core rod is inserted into the cavity, and the hollow core rod has a longitudinal slit along its entire length. And a cylindrical lithium secondary battery satisfying the hollow core rod outer diameter A, the slit width B, and the force 0.1 ⁇ B / A ⁇ 0.6.
  • the cylindrical lithium secondary battery of the present invention When the thickness of the porous heat-resistant layer is represented by C m, the cylindrical lithium secondary battery of the present invention
  • the porous heat-resistant layer is preferably supported on at least one of the two active material layers supported on both sides of the core material in at least one of the positive electrode and the negative electrode.
  • the porous heat-resistant layer preferably contains an insulating filler.
  • the insulating filler also has inorganic acidity.
  • the present invention it is possible to provide a lithium secondary battery excellent in short circuit resistance and heat resistance, and excellent in the balance of battery characteristics in which the capacity reduction due to impact such as falling is unlikely to occur.
  • FIG. 1 is a partial cross-sectional conceptual view of a cylindrical lithium secondary battery of the present invention.
  • FIG. 2 is a perspective view of an example of a hollow core rod.
  • FIG. 3 is a cross-sectional view taken along line III-III in FIG.
  • FIG. 4 is a longitudinal sectional view of a cylindrical lithium secondary battery according to an example of the present invention.
  • the present invention is based on the following three findings.
  • the deformation accompanying charging and discharging becomes smaller than that in the conventional electrode group not having the porous heat-resistant layer. This is considered to be because slippage or misalignment of the electrode and the separator is less likely to cause the surface smoothness of the porous heat-resistant layer to be lower than that of the positive electrode, the negative electrode and the separator.
  • the dimension of the slit of the core rod has a correlation with the force with which the core rod presses the electrode group.
  • the force with which the core rod presses the electrode group has a correlation with the force with which the electrode group presses the side wall of the battery can. Therefore, by optimizing the dimension of the slit, even in the case of using a small deformation electrode group having a porous heat-resistant layer, the electrode group can press the side wall of the battery can with an appropriate force.
  • FIG. 1 conceptually shows a part of a cylindrical lithium secondary battery of the present invention.
  • the positive electrode 13 has a strip-shaped positive electrode core material 11 and a positive electrode active material layer 12 supported on both sides thereof.
  • the negative electrode 16 has a strip-like negative electrode core material 14 and a negative electrode active material layer 15 supported on both sides thereof.
  • the porous heat-resistant layer 18 is supported on the surface of the negative electrode active material layer 15.
  • the porous heat resistant layer 18 plays a role of preventing the expansion of the short circuit part at the time of the internal short circuit.
  • the positive electrode 13 and the negative electrode 16 are wound together with a strip-like separator 17 and a porous heat-resistant layer 18 interposed therebetween to constitute an electrode group.
  • the exposed portion 14a of the negative electrode core member is disposed at the outermost periphery of the electrode assembly.
  • the electrode group is accommodated in a cylindrical battery can 19.
  • a hollow core rod 10 is inserted in a hollow portion at the center of the electrode assembly.
  • FIG. 2 is a perspective view showing an example of a hollow core rod.
  • the core rod 20 has a longitudinal slit 20a along its entire length.
  • the slit 20a has a function of introducing the non-aqueous electrolyte into the electrode group from the inside.
  • FIG. 3 is a cross-sectional view of the core rod 20 taken along line III-III in FIG.
  • the cross section of the core rod 20 is a substantially circular ring shape.
  • the slit 20a introduces the non-aqueous electrolyte to the electrode group.
  • the function (first function) and the function (the second function) in which the core rod 20 presses the electrode group to the outside are expressed in a well-balanced manner. Therefore, even in the case of using an electrode group in which deformation does not easily occur, the electrode group is pressed against the side wall of the battery can with an appropriate force.
  • the BZA ratio satisfies 0.15 ⁇ B / A ⁇ 0.5
  • the first function and the second function are expressed in a more balanced manner.
  • the outer diameter A is determined in the following manner. First, in the cross section of the core rod 20, a straight line X passing through the center 21 of the slit and the center of gravity 22 of the mandrel 20 is determined. Next, a straight line Y perpendicular to the straight line X and parallel to the cross section of the core rod 20 and passing through the center of gravity 22 of the mandrel 20 is determined. At this time, let the outer diameter of the core rod 20 measured along the straight line Y be an outer diameter A. In addition, when there is a difference between the inner peripheral surface and the outer peripheral surface of the slit width B, the average value of the widths of the inner peripheral surface and the outer peripheral surface is taken as the width B.
  • the width B of the slit When the width B of the slit is too large relative to the outer diameter A and 0.6 ⁇ BZA, the force with which the core rod 20 presses the electrode assembly also acts only partially. Therefore, the drop in capacity due to the impact such as falling becomes remarkable.
  • the slit width B is too small relative to the outer diameter A and B / A ⁇ 0.1, the function of the slit for introducing the non-aqueous electrolyte into the electrode assembly is degraded. Therefore, the penetration of the non-aqueous electrolyte into the electrode group becomes insufficient, and the initial battery capacity decreases. That is, as the BZA ratio is larger (the width of the slit is wider), the effect of the core rod pressing the electrode group is reduced.
  • the smaller the BZA ratio the narrower the slit width), the more difficult it is for the non-aqueous electrolyte to permeate the electrode group.
  • the material constituting the hollow core rod is not particularly limited, but stainless steel, iron and the like are preferable in terms of strength and chemical stability in the battery usage environment.
  • the preferred thickness of the material constituting the hollow core rod is preferably in the range of 0.5 to 0.5 mm from the viewpoint of achieving both strength and caustic, in particular 0.1 to 0.5 mm. .
  • the preferred thickness of the material varies with the type of material.
  • the outer diameter A of the core rod can be appropriately selected according to the design of the battery.
  • the outer diameter A of the core rod is generally 1 to 3 mm.
  • the outer diameter of the core rod be smaller by about 0.5 to 2 mm than the initial diameter of the hollow portion at the center of the electrode assembly. If this difference is less than 0.5 mm, hollow core rods will be inserted into the cavity, and the production yield will drop. Conversely, when this difference exceeds 2 mm, the force with which the core rod presses the electrode assembly also decreases. Therefore, the drop in capacity due to impact such as falling may be noticeable. Note that the diameter of the hollow portion at the center of the electrode group changes due to the repetition of charge and discharge of the battery.
  • the thickness of the porous heat-resistant layer is preferably 0.5 to 20 ⁇ m, more preferably 1 to 10 ⁇ m 2 to 2: particularly preferable LO m 2 to 6 / ⁇ Most preferred.
  • the porous heat-resistant layer has the function of retaining the non-aqueous electrolyte (electrolytic retention). If the porous heat-resistant layer is too thin, the liquid retentivity may be reduced, and the discharge characteristics (particularly high-rate discharge characteristics) may be reduced. On the other hand, when the porous heat-resistant layer is too thick, the liquid retention property is enhanced, but the porous heat-resistant layer becomes brittle. Therefore, there is a possibility that displacement of the electrodes in the electrode group may easily occur due to impact such as falling.
  • the thickness of the porous heat-resistant layer is represented by C ⁇ m
  • the outer diameter A of the hollow core rod, the width B of the slit and the thickness C of the porous heat-resistant layer are 0.2 0
  • CXB It is further desirable to satisfy /A ⁇ 3.5. 0.5 ⁇ ⁇ ⁇ ⁇ (CXB) / A ⁇ 3.
  • (C X B) / A ⁇ 0.2 the permeability of the non-aqueous electrolyte to the electrode may be reduced because the slit width B of the core rod thins the porous heat-resistant layer is also small.
  • the BZA ratio is maintained relatively small even when the porous heat-resistant layer is thick. Therefore, the effect of the hollow core rod pressing the electrode group is also maintained relatively large, and even when the porous heat-resistant layer is brittle, the decrease in battery capacity due to impact is less likely to occur. Also. Since the thick porous heat-resistant layer has high liquid retention, good discharge characteristics are maintained even if the slit width is narrowed.
  • the porous heat-resistant layer may be provided only on the surface of the positive electrode active material layer, and may be provided only on the surface of the negative electrode active material layer.
  • the porous heat-resistant layer may be provided on the surface of the positive electrode active material layer and the surface of the negative electrode active material layer. May be However, from the viewpoint of surely avoiding the internal short circuit, it is desirable to provide on the surface of the negative electrode active material layer designed to be larger than the positive electrode active material layer.
  • the porous heat-resistant layer is on one side of the core material It may be provided only on a certain active material layer, or may be provided on the active material layer on both sides of the core material. In addition, it is desirable that the porous heat-resistant layer be adhered to the surface of the active material layer.
  • the porous heat-resistant layer may be in the form of an independent sheet!
  • the porous heat-resistant layer formed in the form of a sheet may be difficult to handle because its mechanical strength is not very high.
  • the porous heat-resistant layer may be provided on the surface of the separator.
  • the separator shrinks under high temperature, it is necessary to pay close attention to the conditions for producing the porous heat-resistant layer. From the viewpoint of eliminating these concerns, it is desirable to provide a porous heat-resistant layer on the surface of the positive electrode active material layer or the negative electrode active material layer.
  • the porous heat-resistant layer preferably contains an insulating filler and a binder.
  • a porous heat-resistant layer is formed by applying a raw material paste containing an insulating filler and a small amount of a binder onto the surface of the electrode active material layer or separator by a method such as doctor blade or die coating, and drying it. It is formed from ⁇ .
  • the raw material paste is prepared by mixing an insulating filler, a binder and a liquid component with a twin screw mixer or the like.
  • aramid, polyamide imide and the like are preferably used.
  • a porous heat-resistant layer containing an insulating filler and a binder is preferable to a film made of a high heat-resistant resin fiber, as it has a higher structural strength due to the action of the binder.
  • the insulating filter it is preferable to use a strong inorganic acid oxide which can also use fibers or beads of high heat resistant resin. Since the inorganic acid precipitate is hard, the distance between the positive electrode and the negative electrode can be maintained within the appropriate range even if the electrode expands during charge and discharge.
  • the inorganic oxides in particular, alumina, silica, magnesia, titanium oxide, zirconia and the like are preferable in that they have high electrochemical stability in the use environment of the lithium secondary battery. These may be used alone or in combination of two or more.
  • the amount of the binding agent is not less than the amount of the insulating material from the viewpoint of maintaining the mechanical strength and securing the ion conductivity. More preferably, 2 to 8 parts by weight of 1 to: LO parts by weight are preferred per 100 parts by weight of the mechanical filter. Most of binders and thickeners have the property of swelling with non-aqueous electrolytes. Therefore, when the amount of the binder exceeds 10 parts by weight, the voids of the porous heat-resistant layer are blocked due to excessive swelling of the binder. Peeling, ion conductivity may be reduced, and battery reaction may be inhibited. On the other hand, the mechanical strength of the porous heat-resistant layer may decrease if the amount of the binder is less than the weight part by weight.
  • the binder to be used for the porous heat-resistant layer is not particularly limited, and examples thereof include poly (vinyl fluoride) (hereinafter referred to as PVDF), polytetrafluoroethylene (hereinafter referred to as PTFE), and polyacrylic acid.
  • PVDF poly (vinyl fluoride)
  • PTFE polytetrafluoroethylene
  • polyacrylic acid based on rubber particles (such as BM- 500B (trade name) manufactured by Nippon Zeon Co., Ltd.) and the like!
  • BM- 500B trade name
  • the thickening agent is not particularly limited, but includes carboxymethylcellulose (hereinafter, abbreviated as CMC), polyethylene oxide (hereinafter, abbreviated as PEO), modified acrylonitrile rubber (eg, BM-720H manufactured by Nippon Zeon Co., Ltd. (trade name) )) Such as preferred.
  • CMC carboxymethylcellulose
  • PEO polyethylene oxide
  • modified acrylonitrile rubber eg, BM-720H manufactured by Nippon Zeon Co., Ltd. (trade name)
  • the porosity of the porous heat-resistant layer containing the insulating filler and the binder is preferably 40 to 80% from the viewpoint of maintaining the mechanical strength and improving the resistance to falling, 65% is more preferred. Since the porous heat-resistant layer has lower surface smoothness than the positive electrode, the negative electrode and the separator, slippage (displacement) of the electrode and the separator is excessively suppressed. Therefore, positional deviation of the electrode group is likely to occur. On the other hand, by controlling the porosity of the porous heat-resistant layer to 40 to 80% and including an appropriate amount of electrolyte in the porous heat-resistant layer, the electrode group expands appropriately. Thus, the electrode assembly presses the side wall of the battery can. The effect of setting the porosity to 40 to 80% and the effect of optimizing the BZA ratio are synergistically exerted to further enhance the drop resistance.
  • the porosity of the porous heat-resistant layer can be controlled by changing the median diameter of the insulating filler, changing the amount of the binder, or changing the drying conditions of the raw material paste. For example, if the drying temperature is increased or the volume of the hot air used for drying is increased, the porosity becomes relatively high.
  • the porosity can be determined by force calculation such as the thickness of the porous heat-resistant layer, the amount of the insulating filler and the binder, and the true specific gravity of the insulating filler and the binder.
  • the thickness of the porous heat-resistant layer can be determined by taking a SEM photograph of the cross section of the electrode plate at several places (for example, 10 places) and calculating the average value of the thickness. Also, determine porosity by mercury porosimetry.
  • the separator is also, for example, a microporous film.
  • the separator may be provided between the porous heat-resistant layer and the positive electrode, or may be provided between the porous heat-resistant layer and the negative electrode.
  • Microporous As the material of the ilum, it is preferable that the polyolefin, which is preferable to use a polyolefin, be polyethylene, polypropylene or the like. Microporous films comprising both polyethylene and polypropylene can also be used.
  • the thickness of the microporous film is preferably 8 to 20 / ⁇ from the viewpoint of maintaining a high capacity design.
  • the positive electrode includes a positive electrode core material and a positive electrode active material layer supported on both sides thereof.
  • the positive electrode core material is in the form of a strip suitable for winding, and may be made of Al, Al alloy or the like.
  • the positive electrode active material layer can contain a positive electrode active material as a necessary component, and can contain a conductive agent, a binder and the like as an optional component. These materials are not particularly limited.
  • a lithium-containing transition metal oxide is preferably used as the positive electrode active material.
  • the lithium-containing transition metal oxides lithium cobaltate and its modified product, lithium nickelate and its modified product, lithium manganate and its modified product, and the like are preferable.
  • the negative electrode includes a negative electrode core material and a negative electrode active material layer supported on both sides thereof.
  • the negative electrode core material is in the form of a strip suitable for winding, and may be Cu, Cu alloy or the like.
  • the negative electrode active material layer can contain a negative electrode active material as a necessary component, and can contain a conductive agent, a binder and the like as an optional component. These materials are not particularly limited. However, various kinds of natural graphite, various kinds of artificial black lead, silicon-containing composite materials such as silicide, lithium metal, various alloy materials and the like are preferably used as the negative electrode active material.
  • binder for the positive electrode or the negative electrode for example, PTFE, PVDF, styrene butadiene rubber, or the like can be used.
  • conductive agent for example, acetylene black, ketjen black (registered trademark), various graphite and the like can be used.
  • the non-aqueous electrolyte is preferably a lithium salt dissolved in a non-aqueous solvent U ,.
  • the lithium salt is preferably, but not limited to, LiPF, LiBF and the like. Lithium salt is used alone
  • the non-aqueous solvent is also not particularly limited, but, for example, ethylene carbonate (EC), dimethyole carbonate (DMC), getinole carbonate (DEC), ethyl methyl carbonate (EMC) and the like are preferably used.
  • Non-aqueous solvents may be used alone or in combination of two or more.
  • the material of the battery can should be electrochemically stable in the operating voltage range of the lithium secondary battery.
  • Lu-tin plating is applied for battery cans.
  • alumina insulating FILLER one 970 g of median diameter 0. 3 m, Nippon Zeon's BM- 720H (modified polyacrylonitrile rubber (NMP solution containing 8 wt 0/0 a binder)) and 375 g, An appropriate amount of NMP was stirred with a double-arm mixer to prepare a raw material paste.
  • the raw material paste was applied to the surface of the negative electrode active material layer, and dried at 120 ° C. for 10 hours under vacuum to form a porous heat-resistant layer with a thickness of 5 m.
  • the porosity of the porous heat-resistant layer was 48%.
  • the porosity is determined by the thickness of the porous heat-resistant layer determined by cross-sectional SEM imaging, the amount of alumina present in the porous heat-resistant layer of a certain area determined by fluorescent X-ray analysis, and the true weight of alumina and binder. The weight ratio of alumina to the binder was calculated.
  • a separator 7 is formed of a 20 ⁇ m-thick polyethylene microporous film in which a positive electrode 5 and a negative electrode 6 having porous heat-resistant layers (not shown) provided on both sides thereof are interposed therebetween.
  • a cylindrical electrode group was formed by winding with Agard (trade name) manufactured by Lugard. Subsequently, the electrode group was inserted into a nickel-plated, iron-made cylindrical battery can 1 (inner diameter: 18 mm). Insulating plates 8a and 8b were disposed above and below the electrode assembly, respectively.
  • One end of a positive electrode lead 5 a was connected to the positive electrode 5, and the other end was welded to the lower surface of a sealing plate 2 having a safety valve.
  • One end of a negative electrode lead 6 a was connected to the negative electrode 6, and the other end was welded to the inner bottom surface of the battery can 1.
  • the hollow core rod 9 was inserted into the central cavity (initial diameter 4 mm) of the electrode assembly.
  • core rod 9 a 0.2 mm-thick cold-rolled stainless steel plate (SUS304-CS) was cut into a width of 58 mm, and a substantially cylindrical cover was used.
  • the sealing plate 2 was disposed at the opening of the battery can 1, and the opening end of the battery can 1 was caulked to the periphery of the sealing plate 2.
  • a cylindrical lithium secondary battery with an inner diameter of 18 mm, a height of 65 mm, and a design capacity of 2000 mAh was completed.
  • A 0.5
  • Made made.
  • Constant voltage charge Charge voltage value 4. 2 VZ charge termination current 100 mA
  • Constant current discharge Discharge current value 2000mAZ discharge termination voltage 3V
  • Constant voltage charge Charge voltage value 4. 2 VZ charge termination current 100 mA
  • Constant current discharge Discharge current value 4000mAZ discharge termination voltage 3V
  • the battery whose initial capacity was measured was charged under the following conditions at 20 ° C.
  • Constant current charge Charge current value 1400mAZ Charge termination voltage 4.2V
  • Constant voltage charge Charge voltage value 4. 2 VZ charge termination current 100 mA
  • the charged battery was dropped 30 times from a height of 16 cm in a 20 ° C. environment, and then discharged under the following conditions to determine the discharge capacity (1 C) after the drop.
  • Constant current discharge Discharge current value 2000mAZ discharge termination voltage 3V
  • the ratio of the discharge capacity (1C) after dropping to the initial discharge capacity (1C) was determined as a percentage, and it is shown as drop resistance.
  • the battery 1 in which the slit width B was too small had a significantly lower initial discharge capacity than the other batteries.
  • the battery 1 was disassembled and the electrode group was observed, it was found that the non-aqueous electrolyte infiltrated into the electrode group unevenly. Since the slit width B is narrow, it is considered that the non-aqueous electrolyte hardly penetrates the electrode group.
  • the drop resistance was significantly reduced.
  • the battery 7 was disassembled and the electrode group was observed, several positional deviations between the positive electrode and the negative electrode were observed. Since the slit width is too large, it is considered that the core rod does not have sufficient pressure to press the electrode group from the inside, and the electrode group can not withstand the impact of a drop.
  • the electrode group has a porous heat-resistant layer
  • the outer diameter A of the core rod and the width B of the slit and the force 0.1 ⁇ B in order to achieve both drop resistance and battery characteristics. It is necessary to satisfy /A ⁇ 0.6.
  • the batteries 48 to 54 not having the porous heat-resistant layer showed remarkable overheating in the nail penetration test. However, the resistance to the drop not related to the slit width B of the core rod was good. Since the electrode group without the porous heat-resistant layer deforms appropriately, it is considered that it was firmly fixed in the battery can. Therefore, even if the battery is dropped, it is considered that the positional deviation of the electrodes in the electrode group is suppressed and the capacity reduction is avoided.
  • the battery 2 provided with the porous heat-resistant layer had a higher initial discharge capacity. This means that even when the slit width is small, the presence of the porous heat-resistant layer improves the discharge characteristics. This is considered to be related to the porous heat-resistant layer having the function of retaining the non-aqueous electrolyte.
  • the batteries 2 and 49 were disassembled and the electrode group was observed. As a result, the distribution of the non-aqueous electrolyte in the electrode group was uniform in the battery 2 than in the battery 49.
  • the cylindrical lithium secondary battery of the present invention is excellent in short circuit resistance, has high safety, and can avoid capacity reduction due to dropping, so that it can be used in all portable devices (for example, portable information terminals, portable electronic devices, etc.). It can be used as a power source of equipment etc.).
  • the application of the cylindrical lithium secondary battery of the present invention is not particularly limited, and the cylindrical lithium secondary battery of the present invention can also be used as a power source for small household power storage devices, motorcycles, electric vehicles, hybrid electric vehicles and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Separators (AREA)

Abstract

La présente invention décrit une batterie secondaire cylindrique au lithium, présentant une excellente résistance au court-circuit, capable d'éviter la réduction de capacitance due à une chute et présentant un excellent équilibre des caractéristiques de batterie. La batterie secondaire cylindrique au lithium comprend un groupe d'électrodes comprenant, tous enroulés, une anode en forme de bande, une cathode en forme de bande et une couche poreuse résistante à la chaleur, ainsi qu'un séparateur interposé entre eux ; l'anode comprend un matériau de cœur d'anode et des matériaux actifs d'anode soutenus du côté opposé, la cathode comprend un matériau de cœur de cathode et des matériaux actifs de cathode soutenus du côté opposé, le groupe d'électrodes possède une partie creuse en son centre, une tige de cœur creuse est insérée dans la partie creuse, la tige de cœur creuse possède une fente occupant toute la longueur et le diamètre extérieur A de la tige de cœur creuse et la largeur B de la fente satisfait à la relation 0,1 ≤ B/A ≤ 0,6.
PCT/JP2006/306459 2005-04-04 2006-03-29 Batterie secondaire cylindrique au lithium WO2006106731A1 (fr)

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EP06730407A EP1768202A1 (fr) 2005-04-04 2006-03-29 Batterie secondaire cylindrique au lithium
CN2006800009067A CN101032044B (zh) 2005-04-04 2006-03-29 圆柱形锂二次电池

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JP2005-107253 2005-04-04
JP2005107253 2005-04-04

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EP (1) EP1768202A1 (fr)
JP (1) JP4839116B2 (fr)
KR (1) KR100828876B1 (fr)
CN (1) CN101032044B (fr)
WO (1) WO2006106731A1 (fr)

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10629947B2 (en) 2008-08-05 2020-04-21 Sion Power Corporation Electrochemical cell
KR20170026653A (ko) 2008-08-05 2017-03-08 시온 파워 코퍼레이션 전기화학 셀에서 힘의 적용
US9054387B2 (en) 2010-04-07 2015-06-09 Medtronic, Inc. Electrode assembly including mandrel having removable portion
US8685557B2 (en) 2010-04-07 2014-04-01 Medtronic, Inc. Electrode assembly including mandrel having a removable portion
WO2011155060A1 (fr) * 2010-06-11 2011-12-15 トヨタ自動車株式会社 Batterie rechargeable au lithium et son procédé de production
US9299971B2 (en) 2010-10-06 2016-03-29 Medtronic, Inc. Common carrier for the integrated mandrel battery assembly
US8832914B2 (en) 2010-10-06 2014-09-16 Medtronic, Inc Coiling device for making an electrode assembly and methods of use
EP2721665B1 (fr) 2011-06-17 2021-10-27 Sion Power Corporation Technique de placage pour électrode
KR101905233B1 (ko) 2011-10-13 2018-10-05 시온 파워 코퍼레이션 전극 구조물 및 그의 제조 방법
US9083053B2 (en) 2011-12-21 2015-07-14 Medtronic, Inc. Through weld interconnect joint
US9005802B2 (en) 2011-12-21 2015-04-14 Medtronic, Inc. Electrode assembly with hybrid weld
KR101437477B1 (ko) 2012-04-20 2014-09-03 최대규 리튬 2차전지용 전극재료, 상기 전극재료를 포함하는 전극구조체 및 상기 전극구조체를 포함하는 2차전지
KR101465167B1 (ko) * 2012-10-11 2014-11-25 주식회사 엘지화학 케이블형 이차전지
KR101991149B1 (ko) 2012-12-19 2019-06-19 시온 파워 코퍼레이션 전극 구조물 및 그의 제조 방법
CN106256034B (zh) 2014-05-01 2019-04-23 锡安能量公司 电极制造方法及相关制品
GB201704292D0 (en) 2017-03-17 2017-05-03 Dyson Technology Ltd Energy storage device
GB201704295D0 (en) 2017-03-17 2017-05-03 Dyson Technology Ltd Energy storage device
GB201704293D0 (en) 2017-03-17 2017-05-03 Dyson Technology Ltd Energy storage device
GB201704294D0 (en) * 2017-03-17 2017-05-03 Dyson Technology Ltd Energy storage device
US10868306B2 (en) 2017-05-19 2020-12-15 Sion Power Corporation Passivating agents for electrochemical cells
CN110945688A (zh) 2017-05-19 2020-03-31 赛昂能源有限公司 用于电化学电池的钝化剂
WO2019107049A1 (fr) * 2017-11-30 2019-06-06 パナソニックＩｐマネジメント株式会社 Batterie secondaire cylindrique
US11978917B2 (en) 2019-11-19 2024-05-07 Sion Power Corporation Batteries with components including carbon fiber, and associated systems and methods
US11791511B2 (en) 2019-11-19 2023-10-17 Sion Power Corporation Thermally insulating compressible components for battery packs
US11929523B2 (en) 2019-11-19 2024-03-12 Sion Power Corporation Batteries, and associated systems and methods
US11984575B2 (en) 2019-11-19 2024-05-14 Sion Power Corporation Battery alignment, and associated systems and methods
WO2021183858A1 (fr) 2020-03-13 2021-09-16 Sion Power Corporation Application de pression à des dispositifs électrochimiques comprenant des solides déformables, et systèmes associés
CN116525971B (zh) * 2023-06-14 2024-02-27 江苏中兴派能电池有限公司 一种带有工字型芯轴的圆柱电池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06187959A (ja) * 1992-12-21 1994-07-08 Toshiba Battery Co Ltd 非水電解液電池
JPH07220759A (ja) * 1994-01-31 1995-08-18 Sony Corp 非水電解液二次電池
JP2003257494A (ja) * 2002-02-28 2003-09-12 Toshiba Corp 非水電解質二次電池

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3143951B2 (ja) * 1991-05-02 2001-03-07 ソニー株式会社 非水電解液二次電池
CN1133221C (zh) * 1995-06-28 2003-12-31 宇部兴产株式会社 非水二次电池
WO1997008763A1 (fr) * 1995-08-28 1997-03-06 Asahi Kasei Kogyo Kabushiki Kaisha Pile et son procede de fabrication
US6385299B1 (en) * 1995-09-12 2002-05-07 British Telecommunications Public Limited Company Line testing in a telecommunications network
JPH09245836A (ja) * 1996-03-08 1997-09-19 Fuji Photo Film Co Ltd 非水電解質二次電池
JP3807528B2 (ja) * 1998-01-16 2006-08-09 古河電池株式会社 円筒形２次電池
JPH11224689A (ja) * 1998-02-04 1999-08-17 Fujitsu Ltd 巻回式リチウム二次電池とその電極巻回体
TW595035B (en) * 2000-08-30 2004-06-21 Sumitomo Chemical Co Separator for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery
JP2002222666A (ja) * 2001-01-25 2002-08-09 Ngk Insulators Ltd リチウム二次電池
KR100736512B1 (ko) * 2003-07-29 2007-07-06 마쯔시다덴기산교 가부시키가이샤 리튬이온 2차전지

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06187959A (ja) * 1992-12-21 1994-07-08 Toshiba Battery Co Ltd 非水電解液電池
JPH07220759A (ja) * 1994-01-31 1995-08-18 Sony Corp 非水電解液二次電池
JP2003257494A (ja) * 2002-02-28 2003-09-12 Toshiba Corp 非水電解質二次電池

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EP1768202A1 (fr) 2007-03-28
KR20070065301A (ko) 2007-06-22
US20060222943A1 (en) 2006-10-05
EP1768202A8 (fr) 2007-07-04
JP4839116B2 (ja) 2011-12-21
KR100828876B1 (ko) 2008-05-09
JP2006313737A (ja) 2006-11-16
CN101032044B (zh) 2011-05-11
CN101032044A (zh) 2007-09-05

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